X-RAY SPECTROMETRY

X-Ray Spectrom. 2006; 35: 154158

Published online 7 April 2006 in Wiley InterScience (www.interscience.wiley.com). DOI: 10.1002/xrs.886
Chemical analysis of phosphate rock using different
methods advantages and disadvantages
Madian Jamil Sa,
1
M. Bhagwanth Rao,
1
K. Surya Prakash Rao
2
and Pradip K. Govil
3
1
University College of Technology, O.U., Hyderabad-500 007, A.P., India
2
Applied Geochemistry (R&T), O.U., Hyderabad-500 007, A.P., India
3
NGRI, Hyderabad-500 007, A.P., India
Received 30 May 2005; Revised 19 December 2005; Accepted 21 December 2005
Many analytical methods are considered for chemical analysis of phosphate rock because the accuracy
of analysis is very important. In the present investigations, spectrophotometric and x-ray spectrometric
methods were used to determine P
2
O
5
whereas SiO
2
, CaO, MgO, Al
2
O
3
and Fe
2
O
3
were determined by
gravimetric and x-ray spectrometric methods. Volumetric and x-ray spectrometry methods are necessary
for uorine determination. The investigations revealed that x-ray spectrometry is a precise and accurate
technique, which is cost effective and so better than other methods. Spectrophotometric, volumetric and
gravimetric methods are expensive, time consuming and laborious. X-ray spectrometry is suggested for
commercial companies using regular analyses to save chemicals, time and labour and to maintain quality.
Copyright 2006 John Wiley & Sons, Ltd.
INTRODUCTION
Several methods are used for the determination of P
2
O
5
,
CaO, SiO
2
, Fe
2
O
3
, Al
2
O
3
, MgO and F contents in phosphate
rocks. However, the most reliable method used in the past
is the spectrophotometric determination of P
2
O
5
. Atomic
absorption spectrometry has been applied to the determina-
tion of MgO, CaO, SiO
2
, Fe
2
O
3
and Al
2
O
3
1
and gravimetric
methods for the determination of P
2
O
5
, CaO, SiO
2
, R
2
O
3
(D Fe
2
O
3
CAl
2
O
3
) and MgO. The potentiometric method
with a uoride-selective electrode has long been used for the
determination of uorine with high accuracy. Fluorine has
also been determined by volumetric methods.
13
However,
these analytical methods are old and outdated for critical
analysis. Major and minor oxides such as SiO
2
, Al
2
O
3
, TiO
2
,
CaO, MgO, KiO
2
, MnO, P
2
O
5
and Fe
2
O
3
and a few selected
trace elements, Zr, Y, Sr, Rb, V, Ba, Cr, Ni, Co, Cu and Zn in
IWG standards AN-G, BE-N and MA-N, were determined
relative to USGS geological reference samples and synthetic
standards by using a PW1400 XRF analyser with a P851
computer system in an attempt to obtain reliable values for
the standards.
4
Further, the technique is extremely useful
for analyses in mining, mineralogy and geology and in envi-
ronmental work and waste material analysis. XRF is a very
useful analytical technique in research and pharmacy.
5
A
method has been developed to determine the major, minor
and trace elements in seamount phosphorite using a modern
XRF spectrometric technique. For elements having an ana-
lytical line lower in energy than the energy of the Fe K line
absorption edge, the inter-element absorption-enhancement
effects were corrected using an inuence coefcient method.
For the other elements, the matrix effects were corrected

Correspondence to: Madian Jamil Sa, University College of

Technology, O.U., Hyderabad-500 007, A.P., India.
E-mail: med so152@yahoo.com
using the ratio of the element peak to the Rh K Compton
peak (for I, the Rh K Compton peak was used instead). The
relative standarddeviationwas <1.0%for the major elements
(except C, Na andCl). The accuracy of this methodwas tested
by evaluating analyses of three certied reference materials.
The direct analysis of major and minor elements in geo-
logical materials by the pressed pellet method without any
chemical procedures makes XRF spectrometry a particularly
environmentally friendly analytical technique.
6
A detailed
chemical characterisation of phosphatised basaltic hyalo-
clastites assigned at Sal Island, Cape Verde archipelago, was
undertaken using synchrotron radiation x-ray uorescence.
7
Two different methods of microanalysis, energy-disper-
sive spectrometry (EDS) and proton-induced x-ray emission
(PIXE), were used to determine the appearance of trace
elements (Zn, Sr and Fe) present in bone at the implantation
site containing the ceramic. The spectra obtained by the PIXE
method showed two regions for each element characterizing
either the bone tissue or the ceramic. The PIXE method was
apparently sufciently sensitive for monitoring the amount
of trace element appearing in bone-implanted material.
8
Modern chemical laboratories use XRF spectrometry for
the analysis of phosphate rock samples. We used the latest
XRF spectrometric and also older conventional methods to
compare the results.
EXPERIMENTAL
Collection and Preparation of Specimens for
Analysis
The standard specimen SRM 120c was designated S
1
.
One specimen of soft phosphate collected fromthe lower
bed in the southeastern side in the Eastern B mines in Syria
was coned and quartered and dried. The fraction 0.015 to
C0.037 mm was selected for wet screening and subjected to
grinding to 300 mesh and this specimen was designated S
2
.
Copyright 2006 John Wiley & Sons, Ltd.
Chemical analysis of phosphate rock 155
Another specimen was collected fromthe tailings located
in the Eastern B mines after primary concentration in the
mines by coning and quartering. The specimen was dried
and thoroughly mixed. The fraction 0.105 to C0.037 mm
was ground to 300 mesh and this specimen was designated
S
3
.
Two specimens (one of them SRM 120c) were homoge-
nizedandgroundto300 meshparticle size andthe resultant
specimen was designated S
4
. One gram of the powdered
specimen (300 mesh) was used with a backing of boric
acid powder. The specimen was pressed by using a Model
TP 2d hydraulic press (Herzog Maschinenfabrik, Osnabruck,
Germany) (DIN EN ISO 9001 certied) to obtain pellets of
40 mm diameter. The pellets were pressed at 20 t pressure
and were subjected to XRF analysis.
Instrumentation
XRFexperiments were carriedout witha MagiXPROsequen-
tial XRFspectrometer (Philips, Eindhoven, The Netherlands).
A dedicated computer was used to carry out the regression
analysis to prepare calibration curves using the standards
120c and 694 with reference specimens provided by the
General Company of Phosphate and Mineral Resources
(GECOPHAM) (Homs, Syria). The numbers and chemical
compositions of the standards are given in Table 1. The
numbers and chemical compositions of the reference spec-
imens provided by GECOPHAM are given in Table 2. The
software in the computer was able to make dead time correc-
tions, background and line overlap corrections and matrix
effects, giving the output directly as the concentration in
weight percentage or in ppmafter converting the counts into
concentration with the help of calibration curves. The con-
ditions under which the instrument was operated and the
parameters for the measurement of each element are listed
in Table 3.
In gravimetric methods, the component to be determined
is separated from other components of the specimen by
precipitation. The weight of the precipitate was determined
after it had been ltered from solution, washed and dried.
2,3
Many processes were tried under controlled conditions, such
as preparation of required reagent, boiling, ltration, wash-
ing the precipitate, continuous agitation and temperature
regulation.
In this work, the P
2
O
5
content was determined using a
BCG spectrophotometer and a standard solution of P
2
O
5
from monopotassium phosphate (potassium dihydrogen
phosphate; KH
2
PO
4
). In this method, P
2
O
5
is determined by
measuring at the wavelength of the specimen with respect to
the wavelength of the standard that is used.
A volumetric method
2
for comparison with the XRF
spectrometric method was applied to the determination of
uorine in the phosphate rock specimens.
RESULTS AND DISCUSSION
The standard 120c supplied by the National Institute of
Standards and Technology (NIST) (Gaithersburg, MD, USA)
was analysed by XRF and other methods (P
2
O
5
was
determined by spectrophotometry, CaO, MgO, R
2
O
3
and
SiO
2
by gravimetry and uorine by the volumetric method)
and the results are given in Table 4. Considering the absolute
errors given by NIST, the Fe
2
O
3
, Al
2
O
3
, MgO, P
2
O
5
, SiO
2
and
CaOcontents determinedbyXRFanalysis are similar tothose
given by NIST. However, in other methods the MgO, P
2
O
5
and CaO contents have absolute errors of 0.07, 0.14 and 0.32,
respectively, while the relative errors are 0.2, 0.004 and 0.006,
respectively. Also, SiO
2
was determined as insoluble residue
(IR) by gravimetric method with a similar result. Almost all
of the impurities in the insoluble residue (IR) other than SiO
2
are volatiles and were evaporated. Moreover, the reagent
used to precipitate SiO
2
will form a complex with uorine
and prevent the reaction between uorine and silica. The
gravimetric method considered insoluble residue as SiO
2
,
which leads to inaccurate results, and it can be seen in
Table 4 that the absolute and relative errors are 0.61 and
0.11, respectively. Using the XRF spectrometry method, the
F content has the absolute and the relative errors of 0.02 and
0.005, respectively. With the gravimetric method the R
2
O
3
(D Al
2
O
3
CFe
2
O
3
) content has absolute and relative errors
of 0.1 and 0.04, respectively. Using the volumetric method,
the F content has absolute and relative errors of 1.2 and 0.31,
respectively.
The specimen S
2
was analysedby XRF andother methods
(the same as for specimen S
1
) and the results are given in
Table 4. Comparison of the results for specimens S
1
and
S
2
showed that the gravimetric and XRF methods gave
close values of P
2
O
5
content. However, again the difference
became large for the uorine and SiO
2
contents.
The specimen S
3
was analysedby XRF andother methods
(the same as for specimens S
1
and S
2
) and the results are
given in Table 4. There is good agreement between the XRF
and volumetric methods for the determination of uorine
content. The other analytes showed signicant differences
and it can be observed that for low grades of phosphate the
Table 1. Chemical composition of the standard references
Number and identication Constituent Concentration (wt%) Constituent Concentration (wt%)
120c (Florida Phosphate Rock) Al
2
O
3
1.30 0.04 Fe
2
O
3
1.08 0.03
CaO 48.02 0.17 P
2
O
5
33.34 0.06
MgO 0.32 0.01 SiO
2
5.5 0.2
F 3.82 0.02
694 (Western Phosphate Rock) Al
2
O
3
1.8 0.1 Fe
2
O
3
0.79 0.06
CaO 43.6 0.4 P
2
O
5
30.2 0.1
MgO 0.33 0.02 SiO
2
11.2 0.4
F 3.2 0.1
Copyright 2006 John Wiley & Sons, Ltd. X-Ray Spectrom. 2006; 35: 154158
156 M. J. Sa et al.
Table 2. Chemical composition of the references provided by GECOPHAM
Number and identication Constituent Concentration (wt%) Constituent Concentration (wt%)
Concentrated Syrian phosphate (Khneiss-1SF) Al
2
O
3
0.2 0.03 Fe
2
O
3
0.34 0.03
CaO 49.3 0.14 P
2
O
5
30.8 0.08
MgO 0.52 0.01 SiO
2
6.8 0.2
F 3.7 0.05
Concentrated Syrian phosphate (Eastern A-2SF) Al
2
O
3
0.4 0.1 Fe
2
O
3
0.28 0.05
CaO 46.4 0.3 P
2
O
5
28.4 0.1
MgO 0.63 0.02 SiO
2
7.5 0.3
F 2.2 0.1
Concentrated Syrian phosphate (Eastern A-3SF) Al
2
O
3
0.3 0.1 Fe
2
O
3
0.47 0.03
CaO 51.9 0.2 P
2
O
5
29.7 0.07
MgO 0.55 0.02 SiO
2
4.3 0.3
F 3.76 0.09
High-grade Syrian phosphate (4SF) Al
2
O
3
0.26 0.04 Fe
2
O
3
0.29 0.06
CaO 51.89 0.13 P
2
O
5
37.19 0.1
MgO 0.33 0.02 SiO
2
5.38 0.4
F 4.03 0.1
Low-grade Syrian phosphate (5SF) Al
2
O
3
0.70 0.02 Fe
2
O
3
0.92 0.04
CaO 52.02 0.17 P
2
O
5
15.42 0.05
MgO 1.25 0.02 SiO
2
7.34 0.2
F 2.97 0.02
Moderate-grade Syrian phosphate (6SF) Al
2
O
3
0.38 0.02 Fe
2
O
3
0.31 0.03
CaO 56.26 0.12 P
2
O
5
23.21 0.05
MgO 0.35 0.02 SiO
2
4.15 0.2
F 3.26 0.08
Low-grade Syrian phosphate (7SF) Al
2
O
3
1.04 0.02 Fe
2
O
3
0.90 0.02
CaO 49.83 0.08 P
2
O
5
19.15 0.04
MgO 1.56 0.02 SiO
2
11.77 0.1
F 3.26 0.05
Moderate-grade Syrian phosphate (8SF) Al
2
O
3
0.36 0.02 Fe
2
O
3
0.26 0.02
CaO 49.86 0.17 P
2
O
5
26.12 0.05
MgO 0.87 0.02 SiO
2
9.44 0.2
F 3.70 0.02
Table 3. XRF analysis and the parameters for the measurement of each element
a
Channel X-tal Collimator (m) Detector kV mA Angle (

2)
Offset Background
Channel 1 (Bg1)
(

2)
Si PE 002-C 550 Flow 40 60 108.9726 2.5206
Al PE 002-C 550 Flow 40 60 144.8606 2.5584
Fe PX9 150 Scint. 30 40 57.4932 0.9596
Mn PX9 150 Scint. 40 80 62.9406 0.9760
Mg PX1 150 Flow 40 60 23.1016 2.3114
Ca PX9 150 Flow 40 70 113.1196 1.0718
Na PX1 550 Flow 40 70 27.9086 2.3812
K PX9 150 Flow 50 40 136.6522 2.0056
Ti PX9 150 Flow 40 70 86.1484 0.9296
F PX1 550 Flow 30 70 43.6202 2.1876
P Ge 111-C 550 Flow 40 70 141.0412 1.9026
a
The other conditions are same for all the elements: anode, rhodium; type, Goniometer; line, K; tube lter, none; measuring
time, 20 s.
Copyright 2006 John Wiley & Sons, Ltd. X-Ray Spectrom. 2006; 35: 154158
Chemical analysis of phosphate rock 157
Table 4. Chemical analyses of S
1
, S
2
, S
3
, S
4a
and S
4
Specimen Chemical analyses P
2
O
5
(%) CaO (%) MgO (%) Fe
2
O
3
(%) Al
2
O
3
(%) SiO
2
(%) F (%)
S
1
XRF method 33.29 48.08 0.32 1.09 1.29 5.59 3.78
Other methods
a
33.14 48.57 0.40 R
2
O
3
D Al
2
O
3
CFe
2
O
3
D 2.55 IR 4.87 2.60
NIST analysis 33.34 0.06 48.02 0.17 0.32 0.01 1.08 0.03 1.30 0.04 5.50 0.02 3.82 0.02
S
2
XRF method 25.66 52.98 0.34 0.26 0.33 7.35 3.48
Other methods
a
25.25 49.59 0.49 R
2
O
3
D Al
2
O
3
CFe
2
O
3
D 0.49 IR 3.23 2.90
S
3
XRF method 17.36 57.72 0.37 0.32 0.46 5.84 2.93
Other methods
a
19.52 51.69 0.49 R
2
O
3
D Al
2
O
3
CFe
2
O
3
D 0.49 IR 3.23 2.90
S
4a
XRF method 23.37 51.17 1.73 0.29 0.39 3.48 3.50
S
4
XRF method 26.63 50.23 1.26 0.59 0.81 4.49 3.61
Calculated
b
26.66 50.13 1.26 0.55 0.69 4.15 3.61
a
P
2
O
5
content was determined by spectrophotometry, CaO, MgO, R
2
O
3
and SiO
2
contents by gravimetry and uorine by the
volumetric method.
b
The contents of S
4
were calculated by component balance using the mass fractions of the specimens.
gravimetric method became inaccurate and gave incorrect
results for the tailings (phosphate rejected in the mines). This
is dolomitic phosphate with a high CaO content of about
57.72% and a high CaO/P
2
O
5
ratio, i.e. 3.32, as found by
XRF, but the gravimetric method gave a 51.69% CaO content
and the CaO/P
2
O
5
ratio of 2.65.
The specimen S
4
was prepared by taking 2 g of a
specimen (S
4a
) analysed by XRF spectrometry and blending
it with 1 g of SRM 120c so that the mass fractions of the
specimens were 0.67 and 0.33, respectively. The specimen
obtained was ground to 300 mesh particle size and
analysed by XRF spectrometry; the chemical analyses of
the resultant specimen (S
4
) are given in Table 4. From
the component material balance and comparison with the
analytical results for the specimen obtained (means between
the experimental and the theoretical results), the same values
for the F and MgO contents were found for both the
calculated and analytical results. The absolute errors for
P
2
O
5
, SiO
2
, Al
2
O
3
, Fe
2
O
3
and CaO were 0.03, 0.34, 0.12, 0.04
and 0.1 and the relative errors were 0.001, 0.08, 0.15, 0.07 and
0.002, respectively.
From the above results, it is clear that the XRF spectro-
metric method gave more accurate results and can be used
for larger range of concentrations and for all major elements
in phosphate rock with a wide range of standards. In the XRF
method the standards used should have a similar chemical
composition to the specimen being analysed, e.g. phosphate
rock with MgO contents >3.00% can not be analysed using
the given standards in this work and it may give wrong
results when dolomite pebbles with higher MgO contents
are analysed. Different standards may be required for spec-
imens obtained from other mines. Table 5 shows the range
of the analyte elements and the range of variations, and it is
evident that XRF shows high accuracy for the major, minor
and trace elements in phosphate rock.
In the volumetric method, several chemical processes
have to be carried out for preparation of chemicals,
calcination, digestion, boiling, distillation, agitation neutral-
ization and titration. The volumetric method is not precise
for the determination of uorine content. The gravimetric
method becomes inaccurate with low-grade phosphate rock
Table 5. Accuracy of XRF for the determined and
undetermined elements
Analyte Range of content (%) Range of variation ()
SiO
2
4.111.2 0.20.4
Al
2
O
3
0.21.8 0.10.04
Fe
2
O
3
0.21.1 0.030.06
MnO 0.010.03 0.0010.002
MgO 0.31.6 0.010.02
CaO 43.656.3 0.080.4
Na
2
O 0.80.5 0.0010.02
K
2
O 0.10.5 0.0040.02
TiO
2
0.10.02 0.0040.006
F 2.24.0 0.020.1
P
2
O
5
15.037.0 0.040.1
(i.e. tailings rejected in the mines) so it cannot be used for
dolomitic phosphate where the P
2
O
5
content is low and that
of CaO is high. Even with high-grade rock (high P
2
O
5
con-
tents) it gives inaccurate results for SiO
2
. The gravimetric
method cannot yield results for Al
2
O
3
and Fe
2
O
3
directly.
However, it gives iron oxide and aluminium oxide together.
For other major components, such as P
2
O
5
, MgO and CaO, it
can be used to determine the concentrations of unknown ele-
ments. The spectrophotometric methodcanbe utilizedfor the
determination of P
2
O
5
only for lowand high concentrations
9
and is unsuitable for intermediate concentrations.
CONCLUSIONS
XRF spectrometry is a rapid, accurate and precise method
for the elemental analysis of phosphate rock specimens and
requires simple and minimal preparation at low cost. It
has the advantage of giving separate concentrations of each
element not related to other contents. XRF spectrometry is
a non-invasive method, which means that the specimens
analysed are not destroyed or changed by exposure to x-rays
andthey canbe savedfor further use as a reference or inother
types of testing. XRF covers a wide range of concentration
using a relatively inexpensive computer for calculations but
it requires a large number of well-analysed samples for
Copyright 2006 John Wiley & Sons, Ltd. X-Ray Spectrom. 2006; 35: 154158
158 M. J. Sa et al.
the initial determination of the coefcients and needs an
expert with a good knowledge of software to operate the
spectrometer.
Commercial companies require XRF spectrometry in
routine analyses instead of the out-of-date methods because
the daily checking of multiple specimens in a short time can
save chemicals, time and labour and can give precise results.
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Copyright 2006 John Wiley & Sons, Ltd. X-Ray Spectrom. 2006; 35: 154158